α-Sulfin and α-Sulfonamino amide derivatives

ABSTRACT

The invention relates to novel pesticidally active α-sulfin- and α-sulfonamino acid amides of the general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein n is a number zero or one, R 1 -R 7  have the meanings given in the specification. R 8  is either hydrogen, (a), (b), (c), (d) or (e) wherein R 11 , R 12 , R 14 , R 15  and R 17  are each independently hydrogen or C 1 -C 4 alkyl, R 13  is C 4 -C 12 alkyl; C 1 -C 12  halogenalkyl; C 3 -C 8  cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl, R 16  is optionally substituted aryl or optionally substituted heteroaryl; and Z is oxygen, sulfur —CR 18 R 19 — or —NR 20 —, wherein R 18 , R 19 , R 20  independently of each other are hydrogen or C 1 -C 4 alkyl. The novel compounds possess plant-protecting properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms

This application is a 371 of PCT/EP01/04207, filed Apr. 11, 2001.

The present invention relates to novel α-sulfin and α-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I

including the optical isomers thereof and mixtures of such isomers, wherein

-   -   n is a number zero or one;     -   R₁ is C₁-C₁₂alkyl, C₁-C₁₂alkyl substituted with C₁-C₄alkoxy,         C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₃-C₈cycloalkyl, cyano,         C₁-C₆alkoxycarbonyl, C₃-C₈alkenyloxycarbonyl or         C₃-C₆alkynyloxycarbonyl; C₃-C₈cycloalkyl; C₂-C₁₂alkenyl;         C₂-C₁₂alkynyl; C₁-C₁₂halogenalkyl; or a group NR₉R₁₀ wherein R₉         and R₁₀ are each independently of the other hydrogen or         C₁-C₆alkyl, or together are tetra- or penta-methylene;     -   R₂ and R₃ are each independently hydrogen; C₁-C₈alkyl;         C₁-C₈alkyl substituted with hydroxy, mercapto, C₁-C₄alkoxy or         C₁-C₄alkylthio: C₃-C₈alkenyl; C₃-C₈alkynyl; C₃-C₈cycloalkyl;         C₃-C₈cycloalkyl-C₁-C₄alkyl; or the two groups R₂ and R₃ together         with the carbon atom to which they are bonded form a three- to         eight-membered hydrocarbon ring;     -   R₄, R₅, R₆ and R₇ are each independently hydrogen or C₁-C₄alkyl;     -   R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each independently hydrogen or         C₁-C₄alkyl,     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl;         optionally substituted aryl or optionally substituted         heteroaryl,     -   R₁₆ is optionally substituted aryl or optionally substituted         heteroaryl, and     -   Z is oxygen, sulfur —CR₁₈R₁₉— or —NR₂₀—, wherein R₁₈, R₁₉ and         R₂₀ independently of each other are hydrogen or C₁-C₄alkyl.

In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.

Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.

The above aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkyl sulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkyl amino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.

In the above definitions “halogen” or the prefix “halo” includes fluorine, chlorine, bromine and iodine.

The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.

Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.

Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.

Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.

A halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl₂, CH₂F, CCl₃, CH₂Cl, CHF₂, CF₃, CH₂CH₂Br, C₂Cl₅, CH₂Br, CHClBr, CF₃CH₂, etc.

Where R₂ and R₃ together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane.

Where R₉ and R₁₀ together with the nitrogen atom to which they are attached form a ring system the ring corresponds to pyrrolidine or piperidine.

The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.

Preferred subgroups of compounds of formula I are those wherein

-   -   n is one; or     -   R₁ is C₁-C₁₂alkyl, C₁-C₁₂alkyl substituted with C₁-C₄alkoxy,         C₁-C₄alkylthio, or C₁-C₄alkylsulfonyl; C₃-C₈cycloalkyl;         C₂-C₁₂alkenyl; C₂-C₁₂alkynyl; C₁-C₁₂halogenalkyl; or a group         NR₉R₁₀ wherein R₉ and R₁₀ are each independently of the other         hydrogen or C₁-C₆alkyl, or together are tetra- or         penta-methylene; or     -   R₁ is C₁-C₁₂alkyl, C₂-C₁₂alkenyl; C₁-C₁₂halogenalkyl; or a group         NR₉R₁₀ wherein R₉ and R₁₀ are each independently of the other         hydrogen or C₁-C₆alkyl; or     -   R₁ is C₁-C₄alkyl, C₂-C₄alkenyl; C₁-C₄halogenalkyl; or         C₁-C₂dialkylamino; or     -   R₁ is C₁-C₄alkyl, vinyl; C₁-C₄halogenalkyl; or dimethylamino; or     -   R₂ is hydrogen and R₃ is C₁-C₈alkyl, C₁-C₈alkyl optionally         substituted by hydroxy, C₁-C₄-alkoxy, mercapto or         C₁-C₄alkylthio; C₃-C₈alkenyl; C₃-C₈alkynyl; C₃-C₈cycloalkyl or         C₃-C₈cycloalkyl-C₁-C₄alkyl; or     -   R₂ is hydrogen and R₃ is C₁-C₄alkyl; C₃-C₄alkenyl or         cyclopropyl; or     -   R₂ is hydrogen and R₃ is C₃-C₄alkyl; allyl or cyclopropyl; or     -   R₂ is hydrogen and R₃ is isopropyl; or     -   R₄ is hydrogen, methyl or ethyl; or     -   R₄ is hydrogen or methyl; or     -   R₄ is hydrogen; or     -   R₅, R₆ and R₇ are each independently hydrogen or methyl; or     -   R₅, R₆ and R₇ are each hydrogen; or     -   R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each independently hydrogen or         methyl; or     -   R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each hydrogen; or     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl;         optionally substituted aryl or optionally substituted heteroaryl         consisting of one or two condensed five or six membered rings         with 1 to 4 identical or different heteroatoms selected from         oxygen, nitrogen or sulfur; or     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl; phenyl,         naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl,         thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl,         pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl,         benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl,         benzoxazolyl or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,         C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₄alkyl, phenyl,         phenyl-C₁-C₄alkyl wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₃-C₈alkenyloxy, C₃-C₈alkynyloxy, C₁-C₈alkoxy-C₁-C₄alkyl,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         C₁-C₈alkylsulfonyl, formyl, C₂-C₈alkanoyl, hydroxy, halogen,         cyano, nitro, amino and C₁-C₈alkylamino, C₁-C₈dialkylamino,         carboxy, C₁-C₈alkoxycarbonyl, C₁-C₈alkenyloxycarbonyl and         C₁-C₈alkynyloxycarbonyl; or     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁-halogenalkyl; C₃-C₈cycloalkyl; phenyl,         naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl         with each of the aromatic ring being optionally substituted by 1         to 3 substituents selected from the group consisting of         C₁-C₈-alkyl, C₂-C₈alkenyl, wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; or     -   R₁₃ is C₄-C₈alkyl; C₁-C₆halogenalkyl; C₃-C₈cycloalkyl; phenyl,         pyridyl, with each of the aromatic ring being optionally         substituted by 1 to 3 substituents selected from the group         consisting of C₁-C₈alkyl, C₁-C₈halogenalkyl, C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; or     -   R₁₆ is optionally substituted aryl or optionally substituted         heteroaryl consisting of one or two condensed five or six         membered rings with 1 to 4 identical or different heteroatoms         selected from oxygen, nitrogen or sulfur; or     -   R₁₆ is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl,         pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl,         pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl,         benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl,         benzoxazolyl or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,         C₃-C₈-cycloalkyl, C₃-C₈cycloalkyl-C₁-C₄alkyl, phenyl,         phenyl-C₁-C₄alkyl wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₃-C₈alkenyloxy, C₃-C₈alkynyloxy, C₁-C₈alkoxy-C₁-C₄alkyl,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         C₁-C₈alkylsulfonyl, formyl, C₂-C₈alkanoyl, hydroxy, halogen,         cyano, nitro, amino, C₁-C₈alkylamino, C₁-C₈dialkylamino,         carboxy, C₁-C₈alkoxycarbonyl, C₁-C₈alkenyloxycarbonyl and         C₁-C₈alkynyloxycarbonyl; or     -   R₁₆ is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl,         triazinyl, or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₂-C₈alkenyl, wherein the         hydrogens of all these substituents may be optionally         substituted by one or more identical or different halogen atoms;         C₁-C₈alkoxy, C₁-C₈halogenalkoxy, C₁-C₈alkylthio,         C₁-C₈halogenalkylthio, halogen, cyano, nitro and         C₁-C₈alkoxycarbonyl; or     -   R₁₆ is phenyl, pyridyl, with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₁-C₈halogenalkyl, C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈-halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; or     -   Z is oxygen, sulfur or —CH₂—; or     -   Z is oxygen.

Further preferred subgroups of the compounds of formula I are those wherein

-   1) R₁ is C₁-C₁₂alkyl, C₁-C₁₂alkyl substituted with C₁-C₄alkoxy,     C₁-C₄alkylthio, or C₁-C₄alkylsulfonyl; C₃-C₈cycloalkyl;     C₂-C₁₂alkenyl; C₂-C₁₂alkynyl; C₁-C₁₂halogenalkyl; or a group NR₉R₁₀     wherein R₉ and R₁₀ are each independently of the other hydrogen or     C₁-C₆alkyl, or together are tetra- or penta-methylene;     -   R₂ is hydrogen and R₃ is C₁-C₈alkyl; C₁-C₈alkyl substituted with         hydroxy, mercapto, C₁-C₄alkoxy or C₁-C₄alkylthio; C₃-C₈alkenyl;         C₃-C₈alkynyl; C₃-C₈cycloalkyl; C₃-C₈cycloalkyl-C₁-C₄alkyl;     -   R₁₃ is C₄-C₁₂-alkyl; C₁-C₁₂-halogenalkyl; C₃-C₈cycloalkyl;         optionally substituted aryl or optionally substituted heteroaryl         consisting of one or two condensed five or six membered rings         with 1 to 4 identical or different heteroatoms selected from         oxygen, nitrogen or sulfur; and     -   R₁₆ is optionally substituted aryl or optionally substituted         heteroaryl consisting of one or two condensed five or six         membered rings with 1 to 4 identical or different heteroatoms         selected from oxygen, nitrogen or sulfur; or -   2) n is one;     -   R₁ is C₁-C₁₂alkyl, C₂-C₁₂alkenyl; C₁-C₁₂halogenalkyl; or a group         NR₉R₁₀ wherein R₉ and R₁₀ are each independently of the other         hydrogen or C₁-C₆alkyl;     -   R₂ is hydrogen and R₃ is C₁-C₄alkyl; C₃-C₄alkenyl or         cyclopropyl;     -   R₄ is hydrogen, methyl or ethyl; or     -   R₅, R₆, R₇, R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each independently         hydrogen or methyl;     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂-halogenalkyl; C₃-C₈-cycloalkyl;         phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl,         pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl,         pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl,         benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl,         benzoxazolyl or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,         C₃-C₈cycloalkyl, C₃-C₈cycloalkyl -C₁-C₄alkyl, phenyl,         phenyl-C₁-C₄alkyl wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₃-C₈alkenyloxy, C₃-C₈alkynyloxy, C₁-C₈alkoxy-C₁-C₄alkyl,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         C₁-C₈alkylsulfonyl, formyl, C₂-C₈alkanoyl, hydroxy, halogen,         cyano, nitro, amino and C₁-C₈alkylamino, C₁-C₈-dialkylamino,         carboxy, C₁-C₈-alkoxycarbonyl, C₁-C₈-alkenyloxycarbonyl and         C₁-C₈alkynyloxycarbonyl;     -   R₁₆ is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl,         pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl,         pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl,         benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl,         benzoxazolyl or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈-alkyl, C₂-C₈alkenyl, C₂-C₈alkynyl,         C₃-C₈cycloalkyl, C₃-C₈cycloalkyl-C₁-C₄alkyl, phenyl,         phenyl-C₁-C₄alkyl wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₃-C₈alkenyloxy, C₃-C₈alkynyloxy, C₁-C₈alkoxy-C₁-C₄alkyl,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         C₁-C₈alkylsulfonyl, formyl, C₂-C₈alkanoyl, hydroxy, halogen,         cyano, nitro, amino and C₁-C₈alkylamino, C₁-C₈dialkylamino,         carboxy, C₁-C₈alkoxycarbonyl, C₁-C₈alkenyloxycarbonyl and         C₁-C₈alkynyloxycarbonyl; and     -   Z is oxygen, sulfur or —CH₂—; or -   3) n is one;     -   R₁ is C₁-C₄alkyl, C₂-C₄alkenyl; C₁-C₄halogenalkyl; or         C₁-C₂-dialkylamino;     -   R₂ is hydrogen and R₃ is C₃-C₄alkyl; allyl or cyclopropyl;     -   R₄ is hydrogen or methyl;     -   R₅, R₆, R₇, R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each hydrogen;     -   R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl; phenyl,         naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl         with each of the aromatic ring being optionally substituted by 1         to 3 substituents selected from the group consisting of         C₁-C₈alkyl, C₂-C₈alkenyl, wherein the hydrogens of all these         substituents may be optionally substituted by one or more         identical or different halogen atoms; C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl;     -   R₁₆ is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl,         triazinyl, or quinolyl with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₂-C₈alkenyl, wherein the         hydrogens of all these substituents may be optionally         substituted by one or more identical or different halogen atoms;         C₁-C₈alkoxy, C₁-C₈halogenalkoxy, C₁-C₈alkylthio,         C₁-C₈halogenalkylthio, halogen, cyano, nitro and         C₁-C₈alkoxycarbonyl; and     -   Z is oxygen, sulfur or —CH₂—; or -   4) n is one;     -   R₁ is C₁-C₄alkyl, vinyl; C₁-C₄halogenalkyl; or dimethylamino;     -   R₂ is hydrogen and R₃ is isopropyl;     -   R₄, R₅, R₆, R₇, R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each hydrogen;     -   R₁₃ is C₄-C₈alkyl; C₁-C₆halogenalkyl; C₃-C₈cycloalkyl; phenyl,         pyridyl, with each of the aromatic ring being optionally         substituted by 1 to 3 substituents selected from the group         consisting of C₁-C₈alkyl, C₁-C₈halogenalkyl, C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈-halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl;     -   R₁₆ is phenyl, pyridyl, with each of the aromatic ring being         optionally substituted by 1 to 3 substituents selected from the         group consisting of C₁-C₈alkyl, C₁-C₈halogenalkyl, C₁-C₈alkoxy,         C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio,         halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; and     -   Z is oxygen.

Preferred individual compounds are:

-   N-(2-{4-[3-(4-chloro-phenyl))-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonyalmino-3-methyl-butyramide, -   N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide, -   N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-methanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide, -   N-(2-{4-[3-(p-tolyl)-prop-2-ynyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,     and -   N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-phenyl]-ethyl}-2-ethanesulfonylamino-3-methyl-butyramide.

Certain α-sulfin- and α-sulfonamino acid derivatives having a different kind of molecular structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160, WO 98/38161 and WO 99/07674).

However, the activity of the known compounds is not always satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, a new kind of microbiocides have been found showing an improved systemic activity in plants against phytopathogenic microorganisms, especially fungi.

The α-sulfin- and α-sulfonamino acid amides of formula I may be obtained according to one of the following processes: a)

An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R₁, n, R₂ and R₃ are as defined for formula I is reacted with an amine of formula III wherein R₄, R₅, R₆, R₇ and R₈ are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B).

Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris (dimethylamino)phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(penta methylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-tetramethyluronium hexafluoro-phosphate or benzotriazol-1-yloxy-tripyrrolidino phosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.

The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethylformamide; nitriles e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.

The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R₂ and R₃ are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R₁ and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).

The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C. b)

The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R₁ and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A. c)

The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R₁, n, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for formula I with a compound of formula VIII wherein R₈ is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D). The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from −80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C. d)

The compounds of formula Ia may also be prepared via formula IX wherein R₁, n, R₂, R₃, R₄, R₅, R₆, R₇, R₁₁, R₁₂ and R₁₃ are defined for formula I by reacting of a phenol of formula VII wherein R₁, n, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for formula I with a compound of formula VIIIa wherein R₁₁, R₁₂ and R₁₃ are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).

The reaction is performed in the same manner as described for step D.

The compounds of formula Ia R₁₁, R₁₂ and R₁₃ is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.

The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinum or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20° C. to +160° C. and at pressures ranging from 1 to 200 bar. aa) The intermediate amines of formula III may be obtained by one of the following processes:

Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).

Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.

Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from −50° C. to +200° C.

Step 4 is the reaction of an aldehyde or a ketone of formula XXIII with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from −20° C. to +150° C.

Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.

Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from −20° C. to +160° C.

Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from −40° C. to +200° C.

In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot. bb) Amines of formula VI can be obtained by the following process:

wherein R is lower alkyl or optionally substituted benzyl.

Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV. The reaction is performed in the same manner as described for step A.

Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII. The reaction is performed in the same manner as described for step D.

Step 10 is the hydrolysis of a carbamate of formula XXXVI. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from −40° C. to +160° C.

The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related technical fields preventively and curatively for the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicida I, activity but also by being especially well tolerated by the treated crop plants.

Surprisingly, it has now been found that for practical purposes the compounds of formula I have a very advantageous biocidal spectrum in the control of phytopathogenic microorganisms, especially fungi. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phyto pathogenic fungi.

The novel compounds of formula I prove to be effective against specific genera of the fungus classes Fungi imperfecti (e.g. Cercospora), Basidio mycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phyto pathogenic fungi. The compounds of formula I can also be used as coatings or dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phyto pathogenic fungi that occur in the soil.

The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.

In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.

Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.

The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.

The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.

Mixing components which are particularly preferred are azoles such as azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202 (trifloxystrobin), picoxystrobin; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halogenmethylthiophthalimides, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as dinocap, nitrothal-isopropyl; organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various, such as AC382042, acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fenhexamid, fentin, ferimzone, fluazinam, flusulfamide, fosetyl-aluminium, hymexazol, IKF-916, iprovalicarb, kasugamycin, methasulfocarb, MON65500, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, RH-7281, RPA 407213, BAS 50001 F, sulfur, SYP-Z071, triazoxide, tricyclazole, triforine, validamycin.

Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.

A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.

The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.

The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA I Example A1.1 (S)-2-Ethanesulfonylamino-N-(2-{4-[3-(4-chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-3-methyl-butyramide

A mixture of 1.0 g of (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide, 1.3 g of toluene-4-sulfonic acid 3-(4-chloro-phenyl)-prop-2-ynyl ester and 4.9 ml of a 1M solution of sodium methoxide in methanol in 25 ml of methanol is heated to reflux for 2 hours. After cooling 200 ml of water is added. The mixture is extracted with ethyl acetate (2×300 ml). The organic layers are washed with brine (2×100 ml), combined, dried (MgSO₄) and evaporated. (S)-N-(2-{4-[3-(4-Chloro-phenyl)-propargyloxy]-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide is obtained which is purified by recrystallization (ethyl acetate/hexane), m.p. 141-142° C.

Analogously to example A1.1 the compounds listed in table A1 are obtained.

-   -   *) Configuration on the α-C-atom in the amino acid moiety; Ph         means phenyl

TABLE A1

No R₁ *) R₃ R₄ R₈ m.p. (° C.) A1.1 CH₃—CH₂— (S) (CH₃)₂CH— H (4-Cl—Ph)—C≡C—CH₂— 141-142 A1.2 CH₃—CH₂— (S) (CH₃)₂CH— H (4-F—Ph)—C≡C—CH₂— 133-134 A1.3 CH₃ (S) (CH₃)₂CH— H (4-Cl—Ph)—C≡C—CH₂— 154-155 A1.4 CH₃ (S) (CH₃)₂CH— H (4-F—Ph)—C≡C—CH₂— 104-105 A1.5 CH₃ (S) (CH₃)₂CH— H (4-Br—Ph)—C≡C—CH₂— 161-164 A1.6 CH₃ (S) (CH₃)₂CH— H (4-CH_(3-Ph)—C≡C—CH) ₂— 110-112 A1.7 CH₃ (S) (CH₃)₂CH— H (4-Cl—Ph)—CH═CH—CH₂— 144-145 A1.8 CH₃ (S) (CH₃)₂CH— H (4-Cl—Ph)—CH₂—CH₂—CH₂— 176-177 A1.9 CH₃ (S) (CH₃)₂CH— H (3-CF₃—Ph)—CH₂ 147-153

Example A2.1 (S)-2-Ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide

18.6 g of (S)-N-[2-(4-benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide and 16.8 g of palladium (5% on charcoal) in 400 ml of tetrahydrofuran are shaken under a hydrogen atmosphere at +30 to +−35° C. and at normal pressure for 5 hours. The reaction mixture is filtered and evaporated. (S)-2-ethanesulfonylamino-N-[2-(4-hydroxy-phenyl)-ethyl]-3-methyl-butyramide is obtained in form of an oil [MS (m/e): 329 (M+H)⁺].

Analogously to example A2.1 the compounds listed in table A2 are obtained.

-   -   *) Configuration on the α-C-atom in the amino acid moiety; Ph         means phenyl

TABLE A2

No R₁ *) R₃ R₄ m.p. (° C.) A2.1 CH₃—CH₂— (S) (CH₃)₂CH— H Oil A2.2 CH₃ (S) (CH₃)₂CH— H 120-121 *) Configuration of the amino acid moiety

Example A3.1 (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide

15 g of (S)-2-ethanesulfonylamino-3-methyl-butyric acid, 10.3 g of thionyl chloride and N,N-dimethylformamide (2 drops) in toluene (75 ml) are refluxed for 2 hours. The solvent is then evaporated. To the resulting residue 100 ml of toluene is added. The mixture is then evaporated to dryness again. The residue is dissolved in dioxane (100 ml) and added to a mixture of 2-(4-benzyloxy-phenyl)-ethylamine (15.3 g) and triethylamine (7.2 g) in dioxane (100 ml). The reaction mixture is stirred at room temperature over night. Water (400 ml) is added. It is extracted with ethyl acetate (2×500 ml). The organic layers are washed with hydrochloric acid (80 ml, 1M solution) and brine (2×100 ml), dried (MgSO₄) and evaporated. (S)-N-[2-(4-Benzyloxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide which is purified by recrystallization (ethyl acetate/hexane), m.p. 133-134° C.

Analogously to example A3.1 the compounds listed in table A3 are obtained.

-   -   *) Configuration on the α-C-atom in the amino acid moiety; Ph         means phenyl

TABLE A3

No R₁ *) R₃ R₄ m.p. (° C.) A3.1 CH₃—CH₂— (S) (CH₃)₂CH— H 133-134 A3.2 CH₃ (S) (CH₃)₂CH— H 153-154 *) Configuration of the amino acid moiety

Analogously to the above Examples the following compounds of Tables 1 to 13 may be prepared. In the tables Ph means phenyl.

TABLE 1 Compounds represented by the Formula I.1 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.1

TABLE 2 Compounds represented by the Formula I.2 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.2

TABLE 3 Compounds represented by the Formula I.3 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.3

TABLE 4 Compounds represented by the Formula I.4 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.4

TABLE 5 Compounds represented by the Formula I.5 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.5

TABLE 6 Compounds represented by the Formula I.6 where the combination of the groups R₁, R₃ and R₈ corresponds to each row in table A. I.6

TABLE A No. R₁ R₃ R₈ 001 CH₃— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 002 CH₃—CH₂— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 003 (CH₃)₂N— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 004 CH₃—CH₂—CH₂— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 005 (CH₃)₂CH— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 006 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 007 CH₃— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 008 CH₃—CH₂— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 009 (CH₃)₂N— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 010 CH₃—CH₂—CH₂— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 011 (CH₃)₂CH— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 012 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— CH₃—(CH₂ )₃—C≡C—CH₂— 013 CH₃— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 014 CH₃—CH₂— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 015 (CH₃)₂N— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 016 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 017 (CH₃)₂CH— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 018 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 019 CH₃—

CH₃—(CH₂ )₃—C≡C—CH₂— 020 CH₃—CH₂—

CH₃—(CH₂ )₃—C≡C—CH₂— 021 (CH₃)₂N—

CH₃—(CH₂ )₃—C≡C—CH₂— 022 CH₃—CH₂—CH₂—

CH₃—(CH₂ )₃—C≡C—CH₂— 023 (CH₃)₂CH—

CH₃—(CH₂ )₃—C≡C—CH₂— 024 Cl—CH₂—CH₂—CH₂—

CH₃—(CH₂ )₃—C≡C—CH₂— 025 CH₃— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 026 CH₃—CH₂— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 027 (CH₃)₂N— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 028 CH₃—CH₂—CH₂— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 029 (CH₃)₂CH— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 030 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 031 CH₃— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 032 CH₃—CH₂— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 033 (CH₃)₂N— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 034 CH₃—CH₂—CH₂— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 035 (CH₃)₂CH— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 036 Cl—CH₂—CH₂—CH₂— CH═C—CH₂— CH₃—(CH₂ )₃—C≡C—CH₂— 037 CH₃— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 038 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 039 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 040 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 041 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 042 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— CH₃—(CH₂ )₃—C≡C—CH₂— 045 CH₃— CH₃—CH₂—

046 CH₃—CH₂— CH₃—CH₂—

047 (CH₃)₂N— CH₃—CH₂—

048 CH₃—CH₂—CH₂— CH₃—CH₂—

049 (CH₃)₂CH— CH₃—CH₂—

050 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—

51 CH₃— (CH₃)₂CH—

052 CH₃—CH₂— (CH₃)₂CH—

053 (CH₃)₂N— (CH₃)₂CH—

054 CH₃—CH₂—CH₂— (CH₃)₂CH—

055 (CH₃)₂CH— (CH₃)₂CH—

056 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH—

057 CH₃— CH₃—CH₂—CH₂—

058 CH₃—CH₂— CH₃—CH₂—CH₂—

059 (CH₃)₂N— CH₃—CH₂—CH₂—

060 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂—

061 (CH₃)₂CH— CH₃—CH₂—CH₂—

062 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂—

063 CH₃—

064 CH₃—CH₂—

065 (CH₃)₂N—

066 CH₃—CH₂—CH₂—

067 (CH₃)₂CH—

068 Cl—CH₂—CH₂—CH₂—

069 CH₃— CH₂═CH—CH₂—

070 CH₃—CH₂— CH₂═CH—CH₂—

071 (CH₃)₂N— CH₂═CH═CH₂—

072 CH₃—CH₂—CH₂— CH₂═CH—CH₂—

073 (CH₃)₂CH— CH₂═CH—CH₂—

074 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂—

075 CH₃— CH═C—CH₂—

076 CH₃—CH₂— CH≡C—CH₂—

077 (CH₃)₂N— CH≡C—CH₂—

078 CH₃—CH₂—CH₂— CH≡C—CH₂—

079 (CH₃)₂CH— CH≡C—CH₂—

080 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂—

081 CH₃— CH₃—CH₂—CH(CH₃)—

082 CH₃—CH₂— CH₃—CH₂—CH(CH₃)—

083 (CH₃)₂N— CH₃—CH₂—CH(CH₃)—

084 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)—

085 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)—

086 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)—

087 CH₃— CH₃—CH₂— Ph—C≡C—CH₂— 088 CH₃—CH₂— CH₃—CH₂— Ph—C≡C—CH₂— 089 (CH₃)₂N— CH₃—CH₂— Ph—C≡C—CH₂— 090 CH₃—CH₂—CH₂— CH₃—CH₂— Ph—C≡C—CH₂— 091 (CH₃)₂CH— CH₃—CH₂— Ph—C≡C—CH₂— 092 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— Ph—C≡C—CH₂— 093 CH₃— (CH₃)₂CH— Ph—C≡C—CH₂— 094 CH₃—CH₂— (CH₃)₂CH— Ph—C≡C—CH₂— 095 (CH₃)₂N— (CH₃)₂CH— Ph—C≡C—CH₂— 096 CH₃—CH₂—CH₂— (CH₃)₂CH— Ph—C≡C—CH₂— 097 (CH₃)₂CH— (CH₃)₂CH— Ph—C≡C—CH₂— 098 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— Ph—C≡C—CH₂— 099 CH₃— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 100 CH₃—CH₂— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 101 (CH₃)₂N— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 102 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 103 (CH₃)₂CH— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 104 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— Ph—C≡C—CH₂— 105 CH₃—

Ph—C≡C—CH₂— 106 CH₃—CH₂—

Ph—C≡C—CH₂— 107 (CH₃)₂N—

Ph—C≡C—CH₂— 108 CH₃—CH₂—CH₂—

Ph—C≡C—CH₂— 109 (CH₃)₂CH—

Ph—C≡C—CH₂— 110 Cl—CH₂—CH₂—CH₂—

Ph—C≡C—CH₂— 111 CH₃— CH₂═CH—CH₂— Ph—C≡C—CH₂— 112 CH₃—CH₂— CH₂═CH—CH₂— Ph—C≡C—CH₂— 113 (CH₃)₂N— CH₂═CH—CH₂— Ph—C≡C—CH₂— 114 CH₃—CH₂—CH₂— CH₂═CH—CH₂— Ph—C≡C—CH₂— 115 (CH₃)₂CH— CH₂═CH—CH₂— Ph—C≡C—CH₂— 116 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— Ph—C≡C—CH₂— 117 CH₃— CH≡C—CH₂— Ph—C≡C—CH₂— 118 CH₃—CH₂— CH≡C—CH₂— Ph—C≡C—CH₂— 119 (CH₃)₂N— CH≡C—CH₂— Ph—C≡C—CH₂— 120 CH₃—CH₂—CH₂— CH≡C—CH₂— Ph—C≡C—CH₂— 121 (CH₃)₂CH— CH≡C—CH₂— Ph—C≡C—CH₂— 122 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— Ph—C≡C—CH₂— 123 CH₃— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 124 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 125 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 126 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 127 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 128 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— Ph—C≡C—CH₂— 129 CH₃— CH₃—CH₂— (4—F—Ph)—C≡C—CH₂— 130 CH₃—CH₂— CH₃—CH₂— (4-F—Ph)—C≡C—CH₂— 131 (CH₃)₂N— CH₃—CH₂— (4-F—Ph)—C≡C—CH₂— 132 CH₃—CH₂—CH₂— CH₃—CH₂— (4-F—Ph)—C≡C—CH₂— 133 (CH₃)₂CH— CH₃—CH₂— (4-F—Ph)—C≡C—CH₂— 134 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (4-F—Ph)—C≡C—CH₂— 135 CH₃— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 136 CH₃—CH₂— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 137 (CH₃)₂N— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 138 CH₃—CH₂—CH₂— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 139 (CH₃)₂CH— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 140 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH₂— (4-F—Ph)—C≡C—CH₂— 141 CH₃— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 142 CH₃—CH₂— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 143 (CH₃)₂N— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 144 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 145 (CH₃)₂CH— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 146 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (4-F—Ph)—C≡C—CH₂— 147 CH₃—

(4-F—Ph)—C≡C—CH₂— 148 CH₃—CH₂—

(4-F—Ph)—C≡C—CH₂— 149 (CH₃)₂N—

(4-F—Ph)—C≡C—CH₂— 150 CH₃—CH₂—CH₂—

(4-F—Ph)—C≡C—CH₂— 151 (CH₃)₂CH—

(4-F—Ph)—C≡C—CH₂— 152 Cl—CH₂—CH₂—CH₂—

(4-F—Ph)—C≡C—CH₂— 153 CH₃— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 154 CH₃—CH₂— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 155 (CH₃)₂N— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 156 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 157 (CH₃)₂CH— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 158 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (4-F—Ph)—C≡C—CH₂— 159 CH₃— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 160 CH₃—CH₂— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 161 (CH₃)₂N— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 162 CH₃—CH₂—CH₂— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 163 (CH₃)₂CH— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 164 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— (4-F—Ph)—C≡C—CH₂— 165 CH₃— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 166 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 167 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 168 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 169 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 170 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-F—Ph)—C≡C—CH₂— 171 CH₃— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 172 CH₃—CH₂— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 173 (CH₃)₂N— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 174 CH₃—CH₂—CH₂— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 175 (CH₃)₂CH— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 176 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (4-Cl—Ph)—C≡C—CH₂— 177 CH₃— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 178 CH₃—CH₂— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 179 (CH₃)₂N— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 180 CH₃—CH₂—CH₂— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 181 (CH₃)₂CH— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 182 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— (4-Cl—Ph)—C≡C—CH₂— 183 CH₃— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 184 CH₃—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 185 (CH₃)₂N— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 186 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 187 (CH₃)₂CH— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 188 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—C≡C—CH₂— 189 CH₃—

(4-Cl—Ph)—C≡C—CH₂— 190 CH₃—CH₂—

(4-Cl—Ph)—C≡C—CH₂— 191 (CH₃)₂N—

(4-Cl—Ph)—C≡C—CH₂— 192 CH₃—CH₂—CH₂—

(4-Cl—Ph)—C≡C—CH₂— 193 (CH₃)₂CH—

(4-Cl—Ph)—C≡C—CH₂— 194 Cl—CH₂—CH₂—CH₂—

(4-Cl—Ph)—C≡C—CH₂— 195 CH₃— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 196 CH₃—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 197 (CH₃)₂N— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 198 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 199 (CH₃)₂CH— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 200 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—C≡C—CH₂— 201 CH₃— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 202 CH₃—CH₂— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 203 (CH₃)₂N— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 204 CH₃—CH₂—CH₂— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 205 (CH₃)₂CH— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 206 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— (4-Cl—Ph)—C≡C—CH₂— 207 CH₃— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 208 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 209 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 210 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 211 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 212 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—C≡C—CH₂— 213 CH₃— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 214 CH₃—CH₂— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 215 (CH₃)₂N— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 216 CH₃—CH₂—CH₂— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 217 (CH₃)₂CH— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 218 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (4-Br—Ph)—C≡C—CH₂— 219 CH₃— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 220 CH₃—CH₂— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 221 (CH₃)₂N— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 222 CH₃—CH₂—CH₂— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 223 (CH₃)₂CH— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 224 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— (4-Br—Ph)—C≡C—CH₂— 225 CH₃— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 226 CH₃—CH₂— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 227 (CH₃)₂N— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 228 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 229 (CH₃)₂CH— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 230 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Br—Ph)—C≡C—CH₂— 231 CH₃—

(4-Br—Ph)—C≡C—CH₂— 232 CH₃—CH₂—

(4-Br—Ph)—C≡C—CH₂— 233 (CH₃)₂N—

(4-Br—Ph)—C≡C—CH₂— 234 CH₃—CH₂—CH₂—

(4-Br—Ph)—C≡C—CH₂— 235 (CH₃)₂CH—

(4-Br—Ph)—C≡C—CH₂— 236 Cl—CH₂—CH₂—CH₂—

(4-Br—Ph)—C≡C—CH₂— 237 CH₃— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 238 CH₃—CH₂— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 239 (CH₃)₂N— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 240 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 241 (CH₃)₂CH— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 242 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (4-Br—Ph)—C≡C—CH₂— 243 CH₃— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 244 CH₃—CH₂— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 245 (CH₃)₂N— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 246 CH₃—CH₂—CH₂— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 247 (CH₃)₂CH— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 248 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— (4-Br—Ph)—C≡C—CH₂— 249 CH₃— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 250 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 251 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 252 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 253 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 254 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Br—Ph)—C≡C—CH₂— 255 CH₃— CH₃—CH₂— H 256 CH₃—CH₂— CH₃—CH₂— H 257 (CH₃)₂N— CH₃—CH₂— H 258 CH₃—CH₂—CH₂— CH₃—CH₂— H 259 (CH₃)₂CH— CH₃—CH₂— H 260 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— H 261 CH₃— (CH₃)₂CH— H 262 CH₃—CH₂— (CH₃)₂CH— H 263 (CH₃)₂N— (CH₃)₂CH— H 264 CH₃—CH₂—CH₂— (CH₃)₂CH— H 265 (CH₃)₂CH— (CH₃)₂CH— H 266 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— H 267 CH₃— CH₃—CH₂—CH₂— H 268 CH₃—CH₂— CH₃—CH₂—CH₂— H 269 (CH₃)₂N— CH₃—CH₂—CH₂— H 270 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— H 271 (CH₃)₂CH— CH₃—CH₂—CH₂— H 272 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— H 273 CH₃—

H 274 CH₃—CH₂—

H 275 (CH₃)₂N—

H 276 CH₃—CH₂—CH₂—

H 277 (CH₃)₂CH—

H 278 Cl—CH₂—CH₂—CH₂—

H 279 CH₃— CH₂═CH—CH₂— H 280 CH₃—CH₂— CH₂═CH—CH₂— H 281 (CH₃)₂N— CH₂═CH—CH₂— H 282 CH₃—CH₂—CH₂— CH₂═CH—CH₂— H 283 (CH₃)₂CH— CH₂═CH—CH₂— H 284 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— H 285 CH₃— CH≡C—CH₂— H 286 CH₃—CH₂— CH≡C—CH₂— H 287 (CH₃)₂N— CH≡C—CH₂— H 288 CH₃—CH₂—CH₂— CH≡C—CH₂— H 289 (CH₃)₂CH— CH≡C—CH₂— H 290 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— H 291 CH₃— CH₃—CH₂—CH(CH₃)— H 292 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— H 293 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— H 294 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— H 295 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— H 296 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— H 297 CH₃— CH₃—CH₂— Ph—CH₂— 298 CH₃—CH₂— CH₃—CH₂— Ph—CH₂— 299 (CH₃)₂N— CH₃—CH₂— Ph—CH₂— 300 CH₃—CH₂—CH₂— CH₃—CH₂— Ph—CH₂— 301 (CH₃)₂CH— CH₃—CH₂— Ph—CH₂— 302 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— Ph—CH₂— 303 CH₃— (CH₃)₂CH— Ph—CH₂— 304 CH₃—CH₂— (CH₃)₂CH— Ph—CH₂— 305 (CH₃)₂N— (CH₃)₂CH— Ph—CH₂— 306 CH₃—CH₂—CH₂— (CH₃)₂CH— Ph—CH₂— 307 (CH₃)₂CH— (CH₃)₂CH— Ph—CH₂— 308 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— Ph—CH₂— 309 CH₃— CH₃—CH₂—CH₂— Ph—CH₂— 310 CH₃—CH₂— CH₃—CH₂—CH₂— Ph—CH₂— 311 (CH₃)₂N— CH₃—CH₂—CH₂— Ph—CH₂— 312 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— Ph—CH₂— 313 (CH₃)₂CH— CH₃—CH₂—CH₂— Ph—CH₂— 314 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— Ph—CH₂— 315 CH₃—

Ph—CH₂— 316 CH₃—CH₂—

Ph—CH₂— 317 (CH₃)₂N—

Ph—CH₂— 318 CH₃—CH₂—CH₂—

Ph—CH₂— 319 (CH₃)₂CH—

Ph—CH₂— 320 Cl—CH₂—CH₂—CH₂—

Ph—CH₂— 321 CH₃— CH₂═CH—CH₂— Ph—CH₂— 322 CH₃—CH₂— CH₂═CH—CH₂— Ph—CH₂— 323 (CH₃)₂N— CH₂═CH—CH₂— Ph—CH₂— 324 CH₃—CH₂—CH₂— CH₂═CH—CH₂— Ph—CH₂— 325 (CH₃)₂CH— CH₂═CH—CH₂— Ph—CH₂— 326 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— Ph—CH₂— 327 CH₃— CH≡C—CH₂— Ph—CH₂— 328 CH₃—CH₂— CH≡C—CH₂— Ph—CH₂— 329 (CH₃)₂N— CH≡C—CH₂— Ph—CH₂— 330 CH₃—CH₂—CH₂— CH≡C—CH₂— Ph—CH₂— 331 (CH₃)₂CH— CH≡C—CH₂— Ph—CH₂— 332 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— Ph—CH₂— 333 CH₃— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 334 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 335 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 336 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 337 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 338 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— Ph—CH₂— 339 CH₃— CH₃—CH₂— (4-Cl—Ph)—CH₂— 340 CH₃—CH₂— CH₃—CH₂— (4-Cl—Ph)—CH₂— 341 (CH₃)₂N— CH₃—CH₂— (4-Cl—Ph)—CH₂— 342 CH₃—CH₂—CH₂— CH₃—CH₂— (4-Cl—Ph)—CH₂— 343 (CH₃)₂CH— CH₃—CH₂— (4-Cl—Ph)—CH₂— 344 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (4-Cl—Ph)—CH₂— 345 CH₃— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 346 CH₃—CH₂— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 347 (CH₃)₂N— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 348 CH₃—CH₂—CH₂— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 349 (CH₃)₂CH— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 350 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— (4-Cl—Ph)—CH₂— 351 CH₃— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 352 CH₃—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 353 (CH₃)₂N— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 354 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 355 (CH₃)₂CH— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 356 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (4-Cl—Ph)—CH₂— 357 CH₃—

(4-Cl—Ph)—CH₂— 358 CH₃—CH₂—

(4-Cl—Ph)—CH₂— 359 (CH₃)₂N—

(4-Cl—Ph)—CH₂— 360 CH₃—CH₂—CH₂—

(4-Cl—Ph)—CH₂— 361 (CH₃)₂CH—

(4-Cl—Ph)—CH₂— 362 Cl—CH₂—CH₂—CH₂—

(4-Cl—Ph)—CH₂— 363 CH₃— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 364 CH₃—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 365 (CH₃)₂N— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 366 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 367 (CH₃)₂CH— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 368 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (4-Cl—Ph)—CH₂— 369 CH₃— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 370 CH₃—CH₂— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 371 (CH₃)₂N— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 372 CH₃—CH₂—CH₂— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 373 (CH₃)₂CH— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 374 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— (4-Cl—Ph)—CH₂— 375 CH₃— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 376 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 378 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 379 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 380 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 381 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (4-Cl—Ph)—CH₂— 382 CH₃— CH₃—CH₂— (3-Cl—Ph)—CH₂— 383 CH₃—CH₂— CH₃—CH₂— (3-Cl—Ph)—CH₂— 384 (CH₃)₂N— CH₃—CH₂— (3-Cl—Ph)—CH₂— 385 CH₃—CH₂—CH₂— CH₃—CH₂— (3-Cl—Ph)—CH₂— 386 (CH₃)₂CH— CH₃—CH₂— (3-Cl—Ph)—CH₂— 387 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (3-Cl—Ph)—CH₂— 388 CH₃— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 389 CH₃—CH₂— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 390 (CH₃)₂N— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 391 CH₃—CH₂—CH₂— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 392 (CH₃)₂CH— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 393 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— (3-Cl—Ph)—CH₂— 394 CH₃— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 395 CH₃—CH₂— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 396 (CH₃)₂N— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 397 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 398 (CH₃)₂CH— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 399 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (3-Cl—Ph)—CH₂— 400 CH₃—

(3-Cl—Ph)—CH₂— 401 CH₃—CH₂—

(3-Cl—Ph)—CH₂— 402 (CH₃)₂N—

(3-Cl—Ph)—CH₂— 403 CH₃—CH₂—CH₂—

(3-Cl—Ph)—CH₂— 404 (CH₃)₂CH—

(3-Cl—Ph)—CH₂— 405 Cl—CH₂—CH₂—CH₂—

(3-Cl—Ph)—CH₂— 406 CH₃— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 407 CH₃—CH₂— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 408 (CH₃)₂N— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 409 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 410 (CH₃)₂CH— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 411 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (3-Cl—Ph)—CH₂— 412 CH₃— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 413 CH₃—CH₂— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 414 (CH₃)₂N— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 415 CH₃—CH₂—CH₂— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 416 (CH₃)₂CH— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 417 Cl—CH₂—CH₂—CH₂— CH≡C—CH₂— (3-Cl—Ph)—CH₂— 418 CH₃— CH₃—CH₂—CH(CH₃)— (3-Cl—Ph)—CH₂— 419 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (3-Cl—Ph)—CH₂— 420 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (3-Cl—Ph)—CH₂— 421 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— CH(CH₃)—(3-Cl—Ph)—CH₂— 422 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (3-Cl—Ph)—CH₂— 423 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (3-Cl—Ph)—CH₂— 424 CH₃— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 425 CH₃—CH₂— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 426 (CH₃)₂N— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 427 CH₃—CH₂—CH₂— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 428 (CH₃)₂CH— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 429 Cl—CH₂—CH₂—CH₂— CH₃—CH₂— (3-CF₃—Ph)—CH₂— 430 CH₃— (CH₃)₂CH— (3-CF₃—Ph)—CH₂— 431 CH₃—CH₂— (CH₃)₂CH— (3-CF₃—Ph)—CH₂— 432 (CH₃)₂N— (CH₃)₂CH— (3-CF₃—Ph)—CH₂— 433 CH₃—CH₂—CH₂— (CH₃)₂CH— (3-CF₃—Ph)—CH₂— 434 (CH₃)₂CH— (CH₃)₂CH— (3-CF₃—Ph)—CH₂— 435 Cl—CH₂—CH₂—CH₂— (CH₃)₂CH— (3-CF₃—Ph)-CH₂— 436 CH₃— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 437 CH₃—CH₂— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 438 (CH₃)₂N— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 439 CH₃—CH₂—CH₂— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 440 (CH₃)₂CH— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 441 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH₂— (3-CF₃—Ph)—CH₂— 442 CH₃—

(3-CF₃—Ph)—CH₂— 443 CH₃—CH₂—

(3-CF₃—Ph)—CH₂— 444 (CH₃)₂N—

(3-CF₃—Ph)—CH₂— 445 CH₃—CH₂—CH₂—

(3-CF₃—Ph)—CH₂— 446 (CH₃)₂CH—

(3-CF₃—Ph)—CH₂— 447 Cl—CH₂—CH₂—CH₂—

(3-CF₃—Ph)—CH₂— 448 CH₃— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 449 CH₃—CH₂— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 450 (CH₃)₂N— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 451 CH₃—CH₂—CH₂— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 452 (CH₃)₂CH— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 453 Cl—CH₂—CH₂—CH₂— CH₂═CH—CH₂— (3-CF₃—Ph)—CH₂— 454 CH₃— CH≡C—CH₂— (3-CF₃—Ph)—CH₂— 455 CH₃—CH₂— CH≡C—CH₂— (3-CF₃—Ph)—CH₂— 456 (CH₃)₂N— CH≡C—CH₂— (3-CF₃—Ph)—CH₂— 457 CH₃—CH₂—CH₂— CH≡C—CH₂— (3-CF₃—Ph)—CH₂— 458 (CH₃)₂CH— CH≡C—CH₂— (3-CF₃—Ph)—CH₂— 459 Cl—CH₂—CH₂—CH₂— CH═C—CH₂— (3-CF₃—Ph)—CH₂— 460 CH₃— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂— 461 CH₃—CH₂— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂— 462 (CH₃)₂N— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂— 463 CH₃—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂— 464 (CH₃)₂CH— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂— 465 Cl—CH₂—CH₂—CH₂— CH₃—CH₂—CH(CH₃)— (3-CF₃—Ph)—CH₂—

TABLE 7 Compounds represented by the Formula I.7 where the combination of the groups R₁, and R₃ corresponds to each row in table B. I.7

TABLE 8 Compounds represented by the Formula I.8 where the combination of the groups R₁, and R₃ corresponds to each row in table B.

I.8

TABLE 9 Compounds represented by the Formula I.9 where the combination of the groups R₁, and R₃ corresponds to each row in table B.

I.9

TABLE 10 Compounds represented by the Formula I.10 where the combination of the groups R₁, and R₃ corresponds to each row in table B.

I.10

TABLE 11 Compounds represented by the Formula I.11 where the combination of the groups R₁, and R₃ corresponds to each row in table B.

I.11

TABLE 12 Compounds represented by the Formula I.12 where the combination of the groups R₁, and R₃ corresponds to each row in table B. 1.12

TABLE B No. R₁ R₃ 001 (CH₃—CH₂)₂N— CH₃—CH₂— 002 CH₃—CH₂—(CH₃)N— CH₃—CH₂— 003

CH₃—CH₂— 004 CH₃—(CH₂)₂—CH₂— CH₃—CH₂— 005 (CH₃)₂CH—CH₂— CH₃—CH₂— 006 CH₃—CH₂—(CH₃)CH— CH₃—CH₂— 007 (CH₃)₃C— CH₃—CH₂— 008 CH₂═CH— CH₃—CH₂— 009

CH₃—CH₂— 010 (CH₃—CH₂)₂N— (CH₃)₂CH— 011 CH₃—CH₂—(CH₃)N— (CH₃)₂CH— 012

(CH₃)₂CH— 013 CH₃—(CH₂)₂—CH₂— (CH₃)₂CH— 014 (CH₃)₂CH—CH₂— (CH₃)₂CH— 015 CH₃—CH₂—(CH₃)CH— (CH₃)₂CH— 016 (CH₃)₃C— (CH₃)₂CH— 017 CH₂═CH— (CH₃)₂CH— 018

(CH₃)₂CH— 019 (CH₃—CH₂)₂N— CH₃—CH₂—CH₂ 020 CH₃—CH₂—(CH₃)N— CH₃—CH₂—CH₂ 021

CH₃—CH₂—CH₂ 022 CH₃—(CH₂)₂—CH₂— CH₃—CH₂—CH₂ 023 (CH₃)₂CH—CH₂— CH₃—CH₂—CH₂ 024 CH₃—CH₂—(CH₃)CH— CH₃—CH₂—CH₂ 025 (CH₃)₃C— CH₃—CH₂—CH₂ 026 CH₂═CH— CH₃—CH₂—CH₂ 027

CH₃—CH₂—CH₂ 028 (CH₃—CH₂)₂N— CH₃—CH₂—(CH₃)CH— 029 CH₃—CH₂—(CH₃)N— CH₃—CH₂—(CH₃)CH— 030

CH₃—CH₂—(CH₃)CH— 031 CH₃—(CH₂)₂—CH₂— CH₃—CH₂—(CH₃)CH— 032 (CH₃)₂CH—CH₂— CH₃—CH₂—(CH₃)CH— 033 CH₃—CH₂—(CH₃)CH— CH₃—CH₂—(CH₃)CH— 034 (CH₃)₃C— CH₃—CH₂—(CH₃)CH— 035 CH₂═CH— CH₃—CH₂—(CH₃)CH— 036

CH₃—CH₂—(CH₃)CH— 037 (CH₃—CH₂)₂N—

038 CH₃—CH₂—(CH₃)N—

039

040 CH₃(CH₂)₂—CH₂—

041 (CH₃)₂CH—CH₂—

042 CH₃—CH₂—(CH₃)CH—

043 (CH₃)₃C—

044 CH₂═CH—

045

046 CH₃— HO—CH₂— 047 CH₃—CH₂— HO—CH₂— 048 (CH₃)₂N— HO—CH₂— 049 CH₃—CH₂—CH₂— HO—CH₂— 050 (CH₃)₂CH— HO—CH₂— 051 CH₃—CH₂—(CH₃)CH— HO—CH₂— 052 CH₃— HO—(CH₃)CH— 053 CH₃—CH₂— HO—(CH₃)CH— 054 (CH₃)₂N— HO—(CH₃)CH— 055 CH₃—CH₂—CH₂— HO—(CH₃)CH— 056 (CH₃)₂CH— HO—(CH₃)CH— 057 CH₃—CH₂—(CH₃)CH— HO—(CH₃)CH— 058 CH₃— (CH₃)₃C—O—(CH₃)CH— 059 CH₃—CH₂— (CH₃)₃C—O—(CH₃)CH— 060 (CH₃)₂N— (CH₃)₃C—O—(CH₃)CH— 061 CH₃—CH₂—CH₂— (CH₃)₃C—O—(CH₃)CH— 062 (CH₃)₂CH— (CH₃)₃C—O—(CH₃)CH— 063 CH₃—CH₂—(CH₃)CH— (CH₃)₃C—O—(CH₃)CH— 064 CH₃— CH₃—S—CH₂—CH₂— 065 CH₃—CH₂— CH₃—S—CH₂—CH₂— 066 (CH₃)₂N— CH₃—S—CH₂—CH₂— 067 CH₃—CH₂—CH₂— CH₃—S—CH₂—CH₂— 068 (CH₃)₂CH— CH₃—S—CH₂—CH₂— 069 CH₃—CH₂—(CH₃)CH— CH₃—S—CH₂—CH₂— 070 CH₃— HS—CH₂—CH₂— 071 CH₃—CH₂— HS—CH₂—CH₂— 072 (CH₃)₂N— HS—CH₂—CH₂— 073 CH₃—CH₂—CH₂— HS—CH₂—CH₂— 074 (CH₃)₂CH— HS—CH₂—CH₂— 075 CH₃—CH₂—(CH₃)CH— HS—CH₂—CH₂— 076 CH₃— (CH₃)₃C— 077 CH₃—CH₂— (CH₃)₃C— 078 (CH₃)₂N— (CH₃)₃C— 079 CH₃—CH₂—CH₂— (CH₃)₃C— 080 (CH₃)₂CH— (CH₃)₃C— 081 CH₃—CH₂—(CH₃)CH— (CH₃)₃C—

TABLE 13 Compounds represented by the Formula I.13 where the combination of the group R₈ corresponds to each row in table C.

I.13

TABLE 14 Compounds represented by the Formula I.14 where the combination of the group R₈ corresponds to each row in table C.

I.14

TABLE 15 Compounds represented by the Formula 1.15 where the combination of the group R₈ corresponds to each row in table C. 1.15

TABLE C No. R₈ 001 CH₃—CH₂—C(CH₃)H—C≡C—CH₂— 002 (CH₃)₃C—C≡C—CH₂— 003 (CH₃)₂CH—CH₂—C≡C—CH₂— 004 CH₃—(CH₂)₄—C≡C—CH₂— 005

006

007 (4-CH₃—Ph)—C≡C—CH₂— 008 (2-Cl—Ph)—C≡C—CH₂— 009 (3-Cl—Ph)—C≡C—CH₂— 010 (3-Br—Ph)—C≡C—CH₂— 011 (3-F—Ph)—C≡C—CH₂— 012 (3-CH₃—Ph)—C≡C—CH₂— 013 (2,4-di-Cl—Ph)—C≡C—CH₂— 014 (3,4-di-Cl—Ph)—C≡C—CH₂— 015 (3,4-di-F—Ph)—C≡C—CH₂— 016 (3-CH₃-4-Cl—Ph)—C≡C—CH₂— 017 (3-CH₃-4-Br—Ph)—C≡C—CH₂— 018 (3-CF₃—Ph)—C≡C—CH₂— 019 (4-CF₃O—Ph)—C≡C—CH₂— 020 (4-Et—Ph)—C≡C—CH₂— 021 [4-(CH₃)₃C—Ph]—C≡C—CH₂— 022 (4-CH₂═CH—Ph)—C≡C—CH₂— 023 (4-CH≡C—Ph)—C≡C—CH₂— 024 (4-CH₃—CO—Ph)—C≡C—CH₂— 025 (4-CH₃OOC—Ph)—C≡C—CH₂— 026 (4-CH₃O—Ph)—C≡C—CH₂— 027

028

029

030

031 Ph—(CH₃)CH— 032 Ph—(CH₃)₂C— 033 (3-F—Ph)—CH₂— 034 (4-Br—Ph)—CH₂— 035 (4-J—Ph)—CH₂— 036 (4-CH₃—Ph)—CH₂— 037 (4-CH₃O—Ph)—CH₂— 038 (4-CF₃O—Ph)—CH₂— 039 (4-F—Ph)—CH₂— 040 (2,4-di-F—Ph)—CH₂— 041 (3,4-di-F—Ph)—CH₂— 042 (3,4-di-Br—Ph)—CH₂— 043 (3,4-di-Cl—Ph)—CH₂— 044 (3-Cl-4-CH_(3-Ph)—CH) ₂— 045 (3-CH₃-4-Cl—Ph)—CH₂— 046 (2,4,5-tri-Cl—Ph)—CH₂— 047

048

049

050

051

052

053

054

055

056

057 Ph—CH═CH—CH₂— 058 (4-Cl—Ph)—CH═CH—CH₂— 059 (4-F—Ph)—CH═CH—CH₂— 060 (4-Br—Ph)—CH═CH—CH₂— 061 (3-CF₃—Ph)—CH═CH₂— 062 Ph—CH₂—CH₂— 063 Ph—(CH₂)₂—CH₂— 064 (4-Cl—Ph)—(CH₂)₂—CH₂— 065 (4-Br—Ph)—(CH₂)₂—CH₂— 066 Ph—O—CH₂—CH₂— 067 (4-Cl—Ph)—O—CH₂—CH₂— 068 (4-F—Ph)—O—CH₂—CH₂— 069 (4-Br—Ph)—O—CH₂—CH₂— 070 (3-F—Ph)—O—CH₂—CH₂— 071 (3,4-di-Cl—Ph)—O—CH₂—CH₂— 072 (4-Cl—Ph)—O—(CH₃)CH—CH₂— 073 (3,4-di-Cl—Ph)—O—(CH₃)CH—CH₂— 074 Ph—N(CH₃)—CH₂—CH₂— 075 Ph—N(CH₂—CH₃)—CH₂—CH₂— 076 Ph—S—CH₂—CH₂— 077 (4-Cl—Ph)—S—CH₂—CH₂—

Formulations may be prepared analogously to those described in, for example, WO 95/30651.

BIOLOGICAL EXAMPLES D-1: Action Against Plasmopara viticola (Downy Mildew) on Vines

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by spraying a sporangia suspension (4×10⁴ sporangia/ml) on the lower leaf side of the test plants. After an incubation period of 6 days at +21° C. and 95% r. h. in a greenhouse the disease incidence is assessed.

Compounds of Tables 1 to 15 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

D-2: Action Against Phytophthora (Late Blight) on Tomato Plants

3 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (2×10⁴ sporangia/mI) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Compounds of Tables 1 to 15 exhibit a long-lasting effect against fungus infestation. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

D-3: Action Against Phytophthora (Late Blight) on Potato Plants

5 week old potato plants cv. Bintje are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (14×10⁴ sporangia/ml) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Fungal infestation is effectively controlled with compounds of Tables 1 to 15. Compounds A1.1, A1.2, A1.3, A1.4, A1.5 and A1.6 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%. 

1. α-sulfin- and α-sulfonamino acid amides of formula I

including the optical isomers thereof and mixtures of such isomers, wherein n is a number zero or one; R₁ is C₁-C₁₂alkyl, C₁-C₁₂alkyl substituted with C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl, C₃-C₈cycloalkyl, cyano, C₁-C₆alkoxycarbonyl, C₃-C₆alkenyloxycarbonyl or C₃-C₈alkynyloxycarbonyl; C₃-C₈cycloalkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkynyl; C₁-C₁₂halogenalkyl; or a group NR₉R₁₀ wherein R₉ and R₁₀ are each independently of the other C₁-C₆alkyl, or together are tetra- or penta-methylene; R₂ and R₃ are each independently hydrogen; C₁-C₈alkyl; C₁-C₈alkyl substituted with hydroxy, mercapto, C₁-C₄alkoxy or C₁-C₄alkylthio; C₃-C₈alkenyl; C₃-C₈alkynyl; C₃-C₈cycloalkyl; C₃-C₃cycloalkyl-C₁-C₄alkyl; or the two groups R₂ and R₃ together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring; R₄, R₅, R₆ and R₇ are each independently hydrogen or C₁-C₄alkyl;

R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each independently hydrogen or C₁-C₄alkyl, R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl, R₁₆ is optionally substituted aryl or optionally substituted heteroaryl; and Z is oxygen, sulfur —CR₁₈R₁₉— or —NR₂₀—, wherein R₁₈, R₁₉ and R₂₀ independently of each other are hydrogen or C₁-C₄alkyl.
 2. A compound according to claim 1 wherein n is one.
 3. A compound of formula I according to claim 1 wherein R₁ is C₁-C₁₂alkyl, C₁-C₁₂alkyl substituted with C₁-C₄alkoxy, C₁-C₄alkylthio, or C₁-C₄alkylsulfonyl; C₃-C₈cycloalkyl; C₂-C₁₂alkenyl; C₂-C₁₂alkynyl; C₁-C₁₂halogenalkyl; or a group NR₉R₁₀ wherein R₉ and R₁₀ are each independently of the other hydrogen or C₁-C₆alkyl, or together are tetra- or penta-methylene.
 4. A compound of formula I according to claim 1 wherein R₂ is hydrogen and R₃ is C₁-C₈alkyl, C₁-C₈alkyl, optionally substituted by hydroxy, C₁-C₄alkoxy, mercapto or C₁-C₄alkylthio; C₃-C₈alkenyl; C₃-C₈alkynyl; C₃-C₈cycloalkyl or C₃-C₈cycloalkyl-C₁-C₄alkyl.
 5. A compound of formula I according to claim 1 wherein R₄ is hydrogen, methyl or ethyl.
 6. A compound of formula I according to claim 1 wherein R₅, R₆ and R₇ are each independently hydrogen or methyl.
 7. A compound of formula I according to claim 1 wherein R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each independently hydrogen or methyl.
 8. A compound of formula I according to claim 1 wherein R₁₃ is C₄-C₁₂alkyl; C₁-C₁₂halogenalkyl; C₃-C₈cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
 9. A compound of formula I according to claim 1 wherein R₁₆ is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.
 10. A compound of formula I according to claim 1 wherein Z is oxygen, sulfur or —CH₂—.
 11. A compound of formula I according to claim 1 wherein n is one; R₁ is C₁-C₄alkyl, vinyl; C₁-C₄halogenalkyl; or dimethylamino; R₂ is hydrogen and R₃ is isopropyl; R₄, R₅, R₆, R₇, R₁₁, R₁₂, R₁₄, R₁₅ and R₁₇ are each hydrogen; R₁₃ is C₄-C₈alkyl; C₁-C₆halogenalkyl; C₃-C₈cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C₁-C₈alkyl, C₁-C₈halogenalkyl, C₁-C₈alkoxy, C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio, halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; R₁₆ is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C₁-C₈alkyl, C₁-C₈halogenalky, C₁-C₈alkoxy, C₁-C₈halogenalkoxy, C₁-C₈alkylthio, C₁-C₈halogenalkylthio, halogen, cyano, nitro and C₁-C₈alkoxycarbonyl; and Z is oxygen.
 12. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting a) an amino acid of formula II or a carboxy-activated derivative thereof

 wherein R₁, n, R₂ and R₃ are as defined for formula I is reacted with an amine of formula III

 wherein R₄, R₅, R₆, R₇ and R₈ are as defined for formula I optionally in the presence of a base and optionally in the presence of a diluting agent, or b) an amino acid derivative of formula VI

 wherein R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V

 wherein R₁ and n are as defined for formula I and X is halide, preferentially chlorine or bromine, or c) a phenol of formula VII

 wherein R₁, n, R₂, R₃, R₄, R₅, R₆ and R₇ are as defined for formula I with a compound of formula VIII

 wherein R₈ is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate.
 13. A process for the preparation of a compound of formula Ia

wherein R₁, n, R₂, R₃, R₄, R₅, R₆, R₇, R₁₁, R₁₂ and R₁₃ are defined in claim 1 for formula I which comprises reacting a compound of formula IX

wherein R₁, n, R₂, R₃, R₄, R₅, R₆, R₇, R₁₁, R₁₂ and R₁₃ are defined for formula I with hydrogen.
 14. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 as active ingredient together with a suitable carrier.
 15. A method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, preferably fungal organisms, which comprises the application of a compound of formula I according to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof. 